U.S. patent application number 13/954127 was filed with the patent office on 2014-02-06 for method for producing flame-retardant thermoplastic elastomer composition.
This patent application is currently assigned to SUMITOMO CHEMICAL COMPANY, LIMITED. The applicant listed for this patent is Sumitomo Chemical Company, Limited. Invention is credited to Ryosuke KUROKAWA, Nobuhiro NATSUYAMA.
Application Number | 20140039108 13/954127 |
Document ID | / |
Family ID | 49944095 |
Filed Date | 2014-02-06 |
United States Patent
Application |
20140039108 |
Kind Code |
A1 |
KUROKAWA; Ryosuke ; et
al. |
February 6, 2014 |
METHOD FOR PRODUCING FLAME-RETARDANT THERMOPLASTIC ELASTOMER
COMPOSITION
Abstract
A method is provided for producing a flame retardant
thermoplastic elastomer composition, wherein the method includes
(1) a step of preparing a thermoplastic elastomer composition by
dynamically vulcanizing a thermoplastic elastomer composition
precursor containing (A) an ethylene-.alpha.-olefin-based copolymer
rubber, (B) a propylene-based polymer and (C) a mineral oil-based
softening agent in the presence of (D) a crosslinking agent, and
(2) a step of kneading the thermoplastic elastomer composition, (E)
a halogen-free flame retardant, (F) a zinc oxide, and optionally
(G) a polyhydric compound.
Inventors: |
KUROKAWA; Ryosuke;
(Ichihara-shi, JP) ; NATSUYAMA; Nobuhiro;
(Ichihara-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Sumitomo Chemical Company, Limited |
Tokyo |
|
JP |
|
|
Assignee: |
SUMITOMO CHEMICAL COMPANY,
LIMITED
Tokyo
JP
|
Family ID: |
49944095 |
Appl. No.: |
13/954127 |
Filed: |
July 30, 2013 |
Current U.S.
Class: |
524/377 ;
524/387; 524/432 |
Current CPC
Class: |
C08L 23/16 20130101;
C08L 23/16 20130101; C08L 23/06 20130101; C08K 2003/2296 20130101;
C08K 5/053 20130101; C08L 23/10 20130101; C08K 5/06 20130101; C08K
5/53 20130101; C08L 23/06 20130101; C08K 3/22 20130101; C08L 23/10
20130101; C08K 5/53 20130101; C08K 5/521 20130101; C08K 3/22
20130101 |
Class at
Publication: |
524/377 ;
524/432; 524/387 |
International
Class: |
C08K 3/22 20060101
C08K003/22; C08K 5/06 20060101 C08K005/06; C08K 5/053 20060101
C08K005/053 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 1, 2012 |
JP |
2012-170898 |
Claims
1. A method for producing a flame retardant thermoplastic elastomer
composition, wherein the method comprises a step of preparing a
thermoplastic elastomer composition by dynamically vulcanizing a
thermoplastic elastomer composition precursor comprising 10 to 75%
by weight of (A) an ethylene-.alpha.-olefin-based copolymer rubber,
10 to 50% by weight of (B) a propylene-based polymer and 1 to 60%
by weight of (C) a mineral oil-based softening agent in the
presence of 0.001 to 5 parts by weight of (D) a crosslinking agent
per 100 parts by weight of the thermoplastic elastomer composition
precursor, where the total amount of the
ethylene-.alpha.-olefin-based copolymer rubber (A), the
propylene-based polymer (B) and the mineral oil-based softening
agent (C) is taken as 100% by weight, and a step of kneading the
thermoplastic elastomer composition, (E) a halogen-free flame
retardant and (F) a zinc oxide where the combined amount of the
halogen-free flame retardant (E) and the zinc oxide (F) is 30 to 70
parts by weight per 100 parts by weight of the thermoplastic
elastomer composition precursor.
2. A method for producing a flame retardant thermoplastic elastomer
composition, wherein the method comprises a step of preparing a
thermoplastic elastomer composition by dynamically vulcanizing a
thermoplastic elastomer composition precursor comprising 10 to 75%
by weight of (A) an ethylene-.alpha.-olefin-based copolymer rubber,
10 to 50% by weight of (B) a propylene-based polymer and 1 to 60%
by weight of (C) a mineral oil-based softening agent in the
presence of 0.001 to 5 parts by weight of (D) a crosslinking agent
per 100 parts by weight of the thermoplastic elastomer composition
precursor, where the total amount of the
ethylene-.alpha.-olefin-based copolymer rubber (A), the
propylene-based polymer (B) and the mineral oil-based softening
agent (C) is taken as 100% by weight, and a step of kneading the
thermoplastic elastomer composition, (E) a halogen-free flame
retardant, (F) a zinc oxide and (G) a polyhydric compound where the
combined amount of the halogen-free flame retardant (E) and the
zinc oxide (F) is 30 to 70 parts by weight and the amount of the
polyhydric compound (G) is 0.5 to 10 parts by weight per 100 parts
by weight of the thermoplastic elastomer composition precursor.
3. The method according to claim 1, wherein the halogen-free flame
retardant (E) is a phosphate-based flame retardant.
4. The method according to claim 2, wherein the polyhydric compound
(G) is selected from the group consisting of pentaerythritol,
dipentaerythritol, tripentaerythritol and polypentaerythritol.
5. The method according to claim 1, wherein the flame retardant
thermoplastic elastomer composition produced by the method has a
Shore A durometer hardness of 60 to 95.
6. The method according to claim 2, wherein the halogen-free flame
retardant (E) is a phosphate-based flame retardant.
7. The method according to claim 2, wherein the flame retardant
thermoplastic elastomer composition produced by the method has a
Shore A durometer hardness of 60 to 95.
Description
TECHNICAL FIELD
[0001] The present invention relates to methods for producing
flame-retardant thermoplastic elastomer compositions.
BACKGROUND ART
[0002] Olefin-based thermoplastic elastomer compositions have been
used widely for automotive interior parts, automotive exterior
parts, electrical machinery parts, household appliance parts,
packaging members, agricultural materials, building members, etc.
because they are capable of being processed with a common molding
machine for thermoplastic resins and being recycled and they are
soft (see patent document 1). However, since thermoplastic
elastomers are flammable materials, they must be made flame
retardant for some applications.
[0003] Well known methods for making a synthetic resin flame
retardant include methods in which an inorganic phosphorus-based
flame retardant such as red phosphorus and phosphorus-containing
flame retardants, an organophosphorus flame retardant such as
triaryl phosphate compounds, a halogen-containing flame retardant,
or a metal hydroxide flame retardant is added, and, optionally, a
flame retarding aid such as antimony oxide, a melamine compound is
further added into a synthetic resin. (See patent documents 2 to
4.)
PRIOR ART DOCUMENTS
Patent Documents
[0004] Patent Document 1: JP-A-2003-147133 [0005] Patent Document
2: JP-A-2010-222402 [0006] Patent Document 3: JP-A-2005-60603
[0007] Patent Document 4: JP-A-2008-63458
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0008] In some occasions, a mineral oil-based softening agent is
incorporated into a thermoplastic elastomer composition in order to
improve softness or the like. In order to fully make a
thermoplastic elastomer composition flame retardant with
incorporation of a mineral oil-based softening agent, it was
necessary to incorporate a large amount of the flame retardant into
the thermoplastic elastomer composition. However, the incorporation
of a large amount of the flame retardant into the thermoplastic
elastomer composition may cause deterioration of the composition in
softness, flowability, molding processability, and mechanical
performance, and it was difficult to provide a thermoplastic
elastomer composition superior in flame retardancy while
maintaining these performances.
[0009] The object of the present invention is to provide a
thermoplastic elastomer composition which is superior in flame
retardancy while maintaining softness, flowability, molding
processability, and mechanical performance.
Means for Solving the Problems
[0010] One embodiment of the present invention is a method for
producing a flame retardant thermoplastic elastomer composition,
wherein the method comprises a step of preparing a thermoplastic
elastomer composition by dynamically vulcanizing a thermoplastic
elastomer composition precursor comprising 10 to 75% by weight of
(A) an ethylene-.alpha.-olefin-based copolymer rubber, 10 to 50% by
weight of (B) a propylene-based polymer and 1 to 60% by weight of
(C) a mineral oil-based softening agent in the presence of 0.001 to
5 parts by weight of (D) a crosslinking agent per 100 parts by
weight of the thermoplastic elastomer composition precursor, where
the total amount of the ethylene-.alpha.-olefin-based copolymer
rubber (A), the propylene-based polymer (B) and the mineral
oil-based softening agent (C) is taken as 100% by weight, and a
step of kneading the thermoplastic elastomer composition, (E) a
halogen-free flame retardant and (F) a zinc oxide where the
combined amount of the halogen-free flame retardant (E) and the
zinc oxide (F) is 30 to 70 parts by weight per 100 parts by weight
of the thermoplastic elastomer composition precursor.
[0011] Another embodiment of the present invention is a method for
producing a flame retardant thermoplastic elastomer composition,
wherein the method comprises a step of preparing a thermoplastic
elastomer composition by dynamically vulcanizing a thermoplastic
elastomer composition precursor comprising 10 to 75% by weight of
(A) an ethylene-.alpha.-olefin-based copolymer rubber, 10 to 50% by
weight of (B) a propylene-based polymer and 1 to 60% by weight of
(C) a mineral oil-based softening agent in the presence of 0.001 to
5 parts by weight of (D) a crosslinking agent per 100 parts by
weight of the thermoplastic elastomer composition precursor, where
the total amount of the ethylene-.alpha.-olefin-based copolymer
rubber (A), the propylene-based polymer (B) and the mineral
oil-based softening agent (C) is taken as 100% by weight, and a
step of kneading the thermoplastic elastomer composition, (E) a
halogen-free flame retardant, (F) a zinc oxide and (G) a polyhydric
compound where the combined amount of the halogen-free flame
retardant (E) and the zinc oxide (F) is 30 to 70 parts by weight
and the amount of the polyhydric compound (G) is 0.5 to 10 parts by
weight per 100 parts by weight of the thermoplastic elastomer
composition precursor.
Effect of the Invention
[0012] The present invention provides a thermoplastic elastomer
composition which is superior in flame retardancy while maintaining
softness, flowability, molding processability, and mechanical
performance.
MODE FOR CARRYING OUT THE INVENTION
(Ethylene-.alpha.-Olefin-Based Copolymer Rubber (A))
[0013] The ethylene-.alpha.-olefin-based copolymer rubber (A) is
sometimes called component (A) in this description. The component
(A) is a copolymer having monomer units derived from ethylene
(ethylene units) and monomer units derived from an .alpha.-olefin
having 3 to 10 carbon atoms (units of an .alpha.-olefin having 3 to
10 carbon atoms). Examples of the .alpha.-olefin having 3 to 10
carbon atoms include propylene, 1-butene, 2-methylpropylene,
1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and
1-octene; one or more monomers out of these olefins are used.
Preferred as the .alpha.-olefin having 3 to 10 carbon atoms are
.alpha.-olefins having 3 to 6 carbon atoms, and more preferred are
propylene and 1-butene.
[0014] The component (A) may have, in addition to ethylene units
and units of an .alpha.-olefin having 3 to 10 carbon atoms, monomer
units derived from other monomers. Examples of such monomers
include conjugated dienes having 4 to 8 carbon atoms such as
1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 1,3-pentadiene,
and 2,3-dimethyl-1,3-butadiene; nonconjugated dienes having 5 to 15
carbon atoms such as dicyclopentadiene, 5-ethylidene-2-norbornene,
1,4-hexadiene, 1,5-dicyclooctadiene, 7-methyl-1,6-octadiene, and
5-vinyl-2-norbornene; vinyl ester compounds such as vinyl acetate;
unsaturated carboxylic acid esters such as methyl acrylate, ethyl
acrylate, butyl acrylate, methyl methacrylate, and ethyl
methacrylate; and unsaturated carboxylic acids such as acrylic acid
and methacrylic acid. The component (A) may have monomer units
derived from one or more monomers. Preferable other monomers
include 5-ethylidene-2-norbornene and dicyclopentadiene.
[0015] The content of the ethylene units in the component (A) is 35
to 90% by weight, preferably 40 to 80% by weight; the content of
the .alpha.-olefin units having 3 to 10 carbon atoms is 10 to 65%
by weight, preferably 20 to 60% by weight; and the content of
monomer units other than the ethylene units and the .alpha.-olefin
units is 0 to 30% by weight, preferably 0 to 20% by weight, where
the overall amount of the monomer units in the
ethylene-.alpha.-olefin-based copolymer rubber is considered to be
100% by weight.
[0016] Examples of the component (A) include ethylene-propylene
copolymer rubbers, ethylene-1-butene copolymer rubbers,
ethylene-1-hexene copolymer rubbers, ethylene-1-octene copolymer
rubbers, ethylene-propylene-1-butene copolymer rubbers,
ethylene-propylene-1-hexene copolymer rubbers,
ethylene-propylene-1-octene copolymer rubbers,
ethylene-propylene-5-ethylidene-2-norbornene copolymer rubbers,
ethylene-propylene-dicyclopentadiene copolymer rubbers,
ethylene-propylene-1,4-hexadiene copolymer rubbers, and
ethylene-propylene-5-vinyl-2-norbornene copolymer rubbers. The
component (A) may comprise two or more rubbers. Preferred are
ethylene-propylene copolymers or
ethylene-propylene-5-ethylidene-2-norbornene copolymers having the
content of ethylene units of 40 to 80% by weight, the content of
propylene units of 15 to 60% by weight, and the content of
5-ethylidene-2-norbornene units of 0 to 20% by weight.
[0017] The Mooney viscosity (ML.sub.1+4100.degree. C.) of the
component (A) is preferably 5 to 300, more preferably 10 to 200.
When the Mooney viscosity is excessively low, mechanical strength
may be poor, and when the Mooney viscosity is excessively high, the
appearance of a molded article may be damaged. The Mooney viscosity
(ML.sub.1+4100.degree. C.) is measured in accordance with JIS K6300
(1994). (ML.sub.1+4100.degree. C.) has the following meaning:
M: Mooney viscosity, L: a large rotor was used, 100.degree. C.:
measurement temperature, 1+4: a value measured when a rotor was
rotated at 2 rpm for 4 minutes after the sample was heated for 1
minute.
[0018] The intrinsic viscosity of the component (A) measured in
135.degree. C. tetralin is preferably 0.5 dl/g to 8 dl/g, more
preferably 1 dl/g to 6 dl/g. When the intrinsic viscosity is
excessively low, mechanical strength may be poor, and when the
intrinsic viscosity is excessively high, the appearance of a molded
article may be damaged.
[0019] An example of a method for producing the component (A) is a
method comprising copolymerizing ethylene, an .alpha.-olefin, and
optionally other monomers by a conventional polymerization
technique such as slurry polymerization, solution polymerization,
bulk polymerization, and vapor phase polymerization, using a
conventional Ziegler-Natta catalyst or a conventional complex-based
catalyst such as a metallocene type complex and a non-metallocene
type complex.
(Propylene-Based Polymer (B))
[0020] The propylene-based polymer (B) is sometimes called
component (B) in this description. The component (B) is a propylene
homopolymer, a propylene-based random copolymer or a
propylene-based block copolymer. The component (B) may include two
or more such polymers. When the component (B) contains ethylene
units, the content of the ethylene units is less than 35% by
weight, where the total amount of all the monomer units in the
component (B) is taken as 100% by weight.
[0021] Preferred as the above-mentioned propylene-based random
copolymer is (1) a propylene-ethylene random copolymer having the
content of propylene units of 90 to 99.5% by weight and the content
of ethylene units of 0.5 to 10% by weight (the sum total of the
contents of the propylene units and the ethylene units is taken as
100% by weight); (2) a propylene-ethylene-.alpha.-olefin random
copolymer having the content of propylene units of 90 to 99% by
weight, the content of ethylene units of 0.5 to 9.5% by weight, and
the content of units of an .alpha.-olefin having 4 to 10 carbon
atoms of 0.5 to 9.5% by weight (the sum total of the contents of
the propylene units, the ethylene units, and the .alpha.-olefin
units is taken as 100% by weight); or (3) a
propylene-.alpha.-olefin random copolymer having the content of
propylene units of 90 to 99.5% by weight and the content of units
of an .alpha.-olefin having 4 to 10 carbon atoms of 0.5 to 10% by
weight (the sum total of the contents of the propylene units and
the .alpha.-olefin units is taken as 100% by weight).
[0022] The above-mentioned propylene-based block copolymer is a
mixture composed of a first polymer and a second polymer produced
by a production method composed of a step (1) of producing the
first polymer which is a propylene homopolymer or a random
copolymer having propylene units and ethylene units and/or
.alpha.-olefin units, and a step (2) of producing, in the presence
of the first polymer, the second polymer which is a random
copolymer having propylene units and ethylene units and/or
.alpha.-olefin units, wherein the content of monomer units other
than propylene units contained in the second polymer (namely, the
combined content of ethylene units and .alpha.-olefin units) is
larger than the content of monomer units other than propylene units
contained in the first polymer.
[0023] The block copolymer is preferably a polymer including the
first polymer in which the content of monomer units other than
propylene units is 0 to 10% by weight (the overall content of all
the monomer units contained in the first polymer is taken as 100%
by weight), more preferably a polymer including the second polymer
in which the content of monomer units other than propylene units is
20 to 80% by weight (the overall content of all the monomer units
contained in the second polymer is taken as 100% by weight), and
even more preferably a polymer in which the content of the second
polymer is 10 to 35% by weight (the quantity of the block copolymer
is taken as 100% by weight).
[0024] Examples of the above-mentioned .alpha.-olefin having 4 to
10 carbon atoms include linear .alpha.-olefins such as 1-butene,
1-pentene, 1-hexene, 1-octene, and 1-decene; branched
.alpha.-olefins such as 3-methyl-1-butene and 3-methyl-1-pentene;
and combinations of two or more of them.
[0025] In order to improve processability, the melt flow rate (MFR)
of the component (B) measured at 230.degree. C. under a load of
21.18 N in accordance with JIS K7210 is 0.1 to 150 g/10 min, more
preferably 0.1 to 100 g/10 min. Too much of the component (B) may
cause deterioration in strength and compression set resistance,
whereas too little of the component (B) may cause deterioration in
processability.
[0026] Examples of the component (B) include propylene
homopolymers, ethylene-propylene random copolymers,
ethylene-propylene-butene random copolymers, ethylene-propylene
block copolymers, and ethylene-propylene-butene block copolymers.
Especially, propylene homopolymers, ethylene-propylene random
copolymers, and ethylene-propylene block copolymers are
preferred.
[0027] An example of the method for producing the propylene-based
polymer of component (B) is a method comprising homopolymerizing
propylene or copolymerizing propylene and other monomers by a
conventional polymerization technique, such as slurry
polymerization, solution polymerization, bulk polymerization, and
vapor phase polymerization, using a conventional Ziegler-Natta
catalyst or a conventional complex-based catalyst such as a
metallocene type complex and a non-metallocene type complex.
(Mineral Oil-Based Softening Agent (C))
[0028] The mineral oil-based softening agent (C) is sometimes
called component (C). Examples of the component (C) include
high-boiling fractions of petroleum (with an average molecular
weight of 300 to 1500 and a pour point of 0.degree. C. or lower)
such as aromatic mineral oil, naphthenic mineral oil, and
paraffinic mineral oil. Among these, paraffinic mineral oil is
preferred.
[0029] The component (C) may be blended as an extending oil of the
component (A). When the component (A) is an oil extended rubber,
the content of the mineral oil-based softening agent in the
component (A) is preferably 10 to 200 parts by weight, more
preferably 20 to 150 parts by weight, and even more preferably 40
to 120 parts by weight, where the amount of the component (A) is
taken as 100 parts by weight. Too much of the mineral oil-based
softening agent may cause deterioration in strength, whereas too
little of the mineral oil-based softening agent may cause
deterioration in processability.
[0030] A conventional method is used as a method for blending the
component (C) with the component (A). Examples of the method
include a method comprising kneading the component (A) and the
component (C) mechanically using a kneading apparatus such as a
roll and a Banbury mixer, and a method comprising preparing a mixed
liquid by adding a prescribed amount of the component (C) to a
solution of the component (A), and then removing the solvent from
the mixed liquid by a steam stripping method or the like.
[0031] In the present invention, in the production of the
thermoplastic elastomer composition precursor, thermoplastic resin
components other than the components (A) to (C) may optionally be
added so long as they do not run counter to the object of the
present invention. Examples of such additional components include
olefin-based polymers other than the component (A) and the
component (B), and ethylene-based polymers and the like are
preferred.
[0032] The ethylene-based polymer to be used for the present
invention is a polymer having monomer units derived from ethylene
(ethylene units) in an amount of more than 90% by weight but not
more than 100% by weight, where the overall amount of the monomers
in the ethylene-based polymer is taken as 100% by weight.
[0033] Examples of the ethylene-based polymer include ethylene
homopolymers and copolymers having one or more .alpha.-olefin units
having 3 to 10 carbon atoms (e.g., propylene, 1-butene, 1-pentene,
4-methyl-1-pentene, and 1-hexene) and ethylene units. Preferred as
the ethylene-based polymer are high density polyethylene, low
density polyethylene, ethylene-propylene copolymers,
ethylene-1-butene copolymers, ethylene-1-pentene copolymers,
ethylene-4-methyl-1-pentene copolymers, and ethylene-1-hexene
copolymers, and more preferred is high density polyethylene.
[0034] The melt flow rate (measured under a load of 21.18 N at a
temperature of 190.degree. C. in accordance with JIS K6760) of the
ethylene-based polymer is preferably 0.01 to 300 g/10 min, more
preferably 0.1 to 200 g/10 min.
[0035] The high density polyethylene to be used for the present
invention is a polymer having monomer units derived from ethylene
(ethylene units) in an amount of more than 90% by weight but not
more than 100% by weight, where the weight of the polymer is taken
as 100% by weight, the polymer having a density of 940 kg/m.sup.3
or more measured in accordance with JIS K7112.
[0036] The melt flow rates (measured at a temperature of
190.degree. C. under a load of 21.18 N in accordance with JIS
K6760) of the high density polyethylene is preferably 0.01 to 300
g/10 min, more preferably 0.1 to 200 g/10 min, even more preferably
0.5 to 50 g/10 min, and particularly preferably 1 to 10 g/10
min.
[0037] The high density polyethylene can be produced by
conventional polymerization methods using a Ziegler-Natta catalyst,
a metallocene catalyst, or the like as a polymerization catalyst.
Examples of the polymerization method include a solution
polymerization method, a bulk polymerization method, a slurry
polymerization method, and a gas phase polymerization method, and
these may be used in combination.
[0038] The thermoplastic elastomer composition precursor includes
the component (A), the component (B), and the component (C). The
thermoplastic elastomer composition precursor includes, where the
total amount of the component (A), the component (B), and the
component (C) is taken as 100% by weight, the component (A) in an
amount of 10 to 75% by weight, preferably 20 to 60% by weight, and
more preferably 30 to 50% by weight, the component (B) in an amount
of 10 to 50% by weight, preferably 10 to 30% by weight, and more
preferably 20 to 30% by weight, and the component (C) in an amount
of 1 to 60% by weight, preferably 10 to 55% by weight, and more
preferably 20 to 50% by weight.
[0039] Examples of the melt-kneading apparatus to be used for
obtaining the thermoplastic elastomer composition precursor of the
present invention include a mixing roll, which is of an open type,
a Banbury mixer, an extruder, a kneader, and a continuous mixer,
which are of a non-open type. Out of these, the use of a non-open
type apparatus is preferred. In the melt-kneading, it is permitted
to melt-knead at once all components to be kneaded, or it is
permitted to knead some components and then add remaining
components, followed by melt-kneading. The melt-kneading may be
carried out either once or twice or more. The temperature in
melt-kneading is usually 150 to 250.degree. C., and the time is
usually 1 to 30 minutes.
(Crosslinking Agent (D))
[0040] The crosslinking agent (D) is sometimes called component (D)
in this description. Conventional crosslinking agents can be used
as the component (D). Examples of the component (D) include organic
peroxides, sulfur compounds, and alkylphenol resins. Especially,
organic peroxides are preferred.
[0041] Examples of such organic peroxides include conventional
ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl
peroxides, peroxyketals, alkyl peresters, percarbonates,
peroxydicarbonates, and peroxyesters. Examples of specific organic
peroxides include dicumyl peroxide,
2,5-dimethyl-2,5-di(tert-butylperoxy)hexane,
2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne,
1,3-bis(tert-butylperoxyisopropyl)benzene, tert-butyl cumyl
peroxide, di-tert-butyl peroxide,
2,2,4-trimethylpentyl-2-hydroperoxide,
diisopropylbenzohydroperoxide, cumene peroxide, tert-butyl
peroxide, 1,1-di(tert-butylperoxy)3,5,5-trimethylcyclohexane,
1,1-di-tert-butylperoxycyclohexane, isobutyl peroxide,
2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide,
bis-3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl
peroxide, p-chlorobenzoyl peroxide; and combination of two or more
of these organic peroxides.
[0042] The amount of the component (D) is 0.001 to 5 parts by
weight, preferably 0.05 to 2 parts by weight, and more preferably
0.1 to 1 part by weight, relative to 100 parts by weight of the
thermoplastic elastomer composition precursor. Too much of the
component (D) may cause deterioration in processability, whereas
too little of the component (D) may cause deterioration in
mechanical strength.
[0043] In order to improve the degree of crosslinking of the
thermoplastic elastomer composition to be produced, the component
(D) may be combined with a crosslinking aid. Preferable
crosslinking aids are compounds having two or more double bonds.
Examples of the crosslinking aid include peroxide crosslinking
aids, such as N,N-m-phenylenebismaleimide, toluoylene bismaleimide,
p-quinonedioxime, nitrosobenzene, diphenylguanidine, and
trimethylolpropane; polyfunctional vinyl monomers, such as
divinylbenzene and triallyl cyanurate, triallyl isocyanurate,
ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate,
trimethylolpropane trimethacrylate, and allyl methacrylate.
Especially, trimethylolpropane trimethacrylate is preferred.
[0044] The amount of the crosslinking aid is 0.01 to 10 parts by
weight and preferably 0.01 to 5 parts by weight, where the amount
of the thermoplastic elastomer composition precursor is taken as
100 parts by weight.
[0045] The method of the present invention comprises a step of
preparing a thermoplastic elastomer composition by dynamically
vulcanizing a thermoplastic elastomer composition precursor
comprising the component (A), the component (B), the component (C),
and optionally other components, in the presence of the component
(D). The "dynamic vulcanization" in the present invention means the
treatment of melt-kneading a thermoplastic elastomer composition
precursor comprising the component (A), the component (B), the
component (C), and optionally other components, in the presence of
the component (D) under shearing force.
[0046] Examples of the melt-kneading apparatus to be used for
obtaining the thermoplastic elastomer composition of the present
invention include a mixing roll, which is of an open type, a
Banbury mixer, an extruder, a kneader, and a continuous mixer,
which are of a non-open type. Out of these, the use of a non-open
type apparatus is preferred. In the melt-kneading, it is permitted
to melt-knead at once all components to be kneaded, or it is
permitted to knead some components and then add remaining
components, followed by melt-kneading. The melt-kneading may be
carried out either once or twice or more. The temperature in
melt-kneading is usually 150 to 250.degree. C., and the time is
usually 1 to 30 minutes.
(Halogen-Free Flame Retardant (E))
[0047] The halogen-free flame retardant (E) is sometimes called
component (E) in this description. As the component (E), there can
be used a halogen-free flame retardant which is commonly used as a
flame retardant for polyolefin. Specific examples thereof include
hydrated metal compounds such as aluminum hydroxide, magnesium
hydroxide and calcium aluminate; organophosphate compounds such as
triphenyl phosphate, tricresyl phosphate, bisphenol A-bisdiphenyl
phosphate and resorcinol-bisdiphenyl phosphate; phosphate compounds
such as ammonium polyphosphate, melamine polyphosphate, piperazine
polyphosphate, piperazine orthophosphate, melamine pyrophosphate,
piperazine pyrophosphate, melamine polyphosphate, melamine
orthophosphate, calcium phosphate and magnesium phosphate; or
mixtures thereof. Out of these, phosphate compounds are
preferred.
[0048] There can likewise be used compounds named by replacing the
term "melamine" or "piperazine" in the above examples of the
phosphate compound by N,N,N',N'-tetramethyldiaminomethane,
ethylenediamine, N,N'-dimethylethylenediamine,
N,N'-diethylethylenediamine, N,N-dimethylethylenediamine,
N,N-diethylethylenediamine, N,N,N',N'-tetramethylethylenediamine,
N,N,N',N'-diethylethylenediamine, 1,2-propanediamine,
1,3-propanediamine, tetramethylenediamine, pentamethylenediamine,
hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane,
1,9-diaminononane, 1,10-diaminodecane,
trans-2,5-dimethylpiperazine, 1,4-bis(2-aminoethyl)piperazine,
1,4-bis(3-aminopropyl)piperazine, acetoguanamine, acrylic
guanamine, 2,4-diamino-6-nonyl-1,3,5-triazine,
2,4-diamino-6-hydroxy-1,3,5-triazine,
2-amino-4,6-dihydroxy-1,3,5-triazine,
2,4-diamino-6-methoxy-1,3,5-triazine,
2,4-diamino-6-ethoxy-1,3,5-triazine,
2,4-diamino-6-propoxy-1,3,5-triazine,
2,4-diamino-6-isopropoxy-1,3,5-triazine,
2,4-diamino-6-mercapto-1,3,5-triazine,
2-amino-4,6-dimercapto-1,3,5-triazine, ammeline, acetoguanamine,
phthalodiguanamine, melamine cyanurate, melamine pyrophosphate,
butylenediguanamine, norbornenediguanamine, methylenediguanamine,
ethylenedimelamine, trimethylenedimelamine,
tetramethylenedimelamine, hexamethylenedimelamine,
1,3-hexylenedimelamine, etc.
(Zinc Oxide (F))
[0049] The zinc oxide (F) is sometimes called component (F) in this
description.
The component (F) may have been surface treated. Examples of the
component (F) include commercially available products such as zinc
oxide Type II produced by Seido Chemical Industry Co., Ltd., zinc
oxide Type I produced by Mitsui Mining & Smelting Co., Ltd.,
partially coated type zinc oxide produced by Mitsui Mining &
Smelting Co., Ltd., NANO FINE 50 (ultrafine particle zinc oxide
with an average particle diameter of 0.02 .mu.m, produced by Sakai
Chemical Industry Co., Ltd.), and NANO FINE K (ultrafine particle
zinc oxide coated with zinc silicate having an average particle
diameter of 0.02 .mu.m, produced by Sakai Chemical Industry Co.,
Ltd.).
(Mixture of Halogen-Free Flame Retardant and Zinc Oxide)
[0050] A mixture in which a halogen-free flame retardant and zinc
oxide have been mixed beforehand may be used as the component (E)
and the component (F). Preferred as the mixture of a halogen-free
flame retardant and zinc oxide is a mixture of a phosphate and zinc
oxide, and specific examples thereof include "ADK STAB FP-2200"
produced by ADEKA Corporation and "ADK STAB FP-2200S" produced by
ADEKA Corporation.
[0051] One embodiment of the present invention has a step of
kneading the thermoplastic elastomer composition, the halogen-free
flame retardant (E), and the zinc oxide (F). The combined amount of
the component (E) and the component (F) is 30 to 70 parts by
weight, preferably 30 to 60 parts by weight, and more preferably 30
to 50 parts by weight, where the amount of the thermoplastic
elastomer composition precursor used in the production of the
thermoplastic elastomer composition is taken as 100 parts by
weight. Too much of the component (E) or the component (F) may
cause deterioration in processability, whereas too little of the
component (E) or the component (F) may cause deterioration in flame
retardancy.
(Polyhydric Compound (G))
[0052] The polyhydric compound (G) is sometimes called component
(G) in this description. Examples of the component (G) include
pentaerythritol, dipentaerythritol, tripentaerythritol,
polypentaerythritol (degree of condensation .gtoreq.4),
trishydroxyethyl isocyanate, polyethylene glycol, glycerol, starch,
grape sugar, cellulose, and sorbitol. Out of these polyhydric
compounds, polyhydric alcohol compounds are preferable in terms of
high affinity to resin, low solubility in water, and low moisture
absorption, and pentaerythritol, dipentaerythritol,
tripentaerythritol, and polypentaerythritol are more preferred, and
pentaerythritol is especially preferred because of their
particularly low solubility in water and particularly low moisture
absorption.
[0053] Another embodiment of the present invention has a step of
kneading the thermoplastic elastomer composition, the halogen-free
flame retardant (E), the zinc oxide (F), and the polyhydric
compound (G). The amount of the component (E) and the component (F)
is the same as in the above-described embodiment. The amount of the
component (G) is preferably 0.5 to 10 parts by weight, more
preferably 1 to 10 parts by weight, and even more preferably 1 to 5
parts by weight, relative to 100 parts by weight of the
thermoplastic elastomer composition precursor used in the
production of the thermoplastic elastomer composition. Too much of
the component (G) may cause deterioration in the appearance or the
mechanical performance of molded articles, whereas too little of
the component (G) may cause deterioration in flame retardancy.
[0054] In the present invention, other additional components may
optionally be added in addition to the aforementioned components
(A) through (G) so long as they do not run counter to the object of
the present invention. Examples of such additional components
include additives such as inorganic fillers (e.g., talc, calcium
carbonate, and calcined kaolin), organic fillers (e.g., fiber, wood
flour, and cellulose powder), antioxidants (e.g., phenol-based,
sulfur-based, phosphorus-based, lactone-based, and vitamin-based
antioxidants), weathering stabilizers, UV absorbers (e.g.,
benzotriazole-based, tridiamine-based, anilide-based, and
benzophenone-based UV absorbers), heat stabilizers, light
stabilizers (e.g., hindered amine light stabilizers and benzoate
type light stabilizers), antistatic agents, nucleating agents,
pigments, adsorbents (e.g., metal oxides), metal chlorides (e.g.,
ferric chloride and calcium chloride), hydrotalcite, aluminates,
lubricants (e.g., fatty acids, higher alcohols, aliphatic amides,
and aliphatic esters) and silicone compounds. Such additives may be
blended in advance into the components (A), (B), (C), (D), (F), and
(G), followed by the preparation of a flame retardant thermoplastic
elastomer composition, or they may be blended after or during the
melt-kneading of the components (A), (B), (C), (D), (E), (F), and
(G).
[0055] The Shore A durometer hardness (measured in accordance with
JIS K6253) of a flame retardant thermoplastic elastomer composition
obtained using the method of the present invention is preferably 60
to 95, more preferably 60 to 90, and even more preferably 65 to
85.
[0056] Examples of the melt-kneading apparatus to be used for
obtaining the flame retardant thermoplastic elastomer composition
of the present invention include a mixing roll, which is of an open
type, a Banbury mixer, an extruder, a kneader, and a continuous
mixer, which are of a non-open type. Out of these, the use of a
non-open type apparatus is preferred. In the melt-kneading, it is
permitted to melt-knead at once all components to be kneaded, or it
is permitted to knead some components and then add remaining
components, followed by melt-kneading. The melt-kneading may be
carried out either once or twice or more. The temperature in
melt-kneading is usually 150 to 250.degree. C., and the time is
usually 1 to 30 minutes.
[0057] A preferred method for producing the flame retardant
thermoplastic elastomer composition of the present invention
preferred in terms of tensile characteristics and compression set,
includes a method comprising a first kneading step of melt-kneading
the component (A), the component (B), and the component (C),
thereby producing a thermoplastic elastomer composition precursor,
a second kneading step of dynamically vulcanizing the thermoplastic
elastomer composition precursor in the presence of the component
(D), thereby producing a thermoplastic elastomer composition, and a
third kneading step of melt-kneading the thermoplastic elastomer
composition, the component (E), the component (F), and optionally
the component (G), thereby producing a flame retardant
thermoplastic elastomer composition.
[0058] Flame retardant thermoplastic elastomer compositions
obtained using the method of the present invention are shaped into
various molded articles by extrusion process, calendering, or
injection molding using an apparatus in use for the shaping of
common thermoplastic resins.
[0059] Molded articles of a flame retardant thermoplastic elastomer
composition obtained using the method of the present invention are
used for various applications such as automotive interior parts
such as a console box and an instrument panel surface material, and
automotive exterior parts such as a window mall, various electrical
machinery parts, various household appliance parts such as housing
materials and toys, various packaging members, various agricultural
materials, and various building members.
EXAMPLES
[0060] The present invention is hereafter further explained on the
basis of Examples, but the invention is not limited to the
Examples.
Methods for Measuring Physical Properties
(1) Mooney Viscosity (ML.sub.1+4100.degree. C.)
[0061] Measurement was conducted in accordance with JIS K6300.
(2) Melt Flow Rate (MFR)
[0062] Measurement was conducted in accordance with JIS K7210.
Measurement was conducted at a temperature of 230.degree. C. and a
load of 98.07 N for flame retardant thermoplastic elastomer
compositions, at a temperature of 230.degree. C. and a load of
21.18 N for propylene-based polymers, and at a temperature of
190.degree. C. and a load of 21.18 N for ethylene-based
polymers.
(3) Contents of Ethylene Units, Propylene Units, and
5-ethylidene-2-norbornene Units
[0063] Measurement was conducted by infrared spectroscopy.
(4) Hardness
[0064] Shore A durometer hardness was measured in accordance with
JIS K6253.
(5) Compression Set
[0065] Measurement was conducted in accordance with JIS K6262 under
conditions including 70.degree. C., 25% compression, and 22
hours.
(6) Strength at Break and Elongation at Break
[0066] Measurement was conducted using a JIS No. 3 specimen under
conditions including a tensile rate of 200 mm/min in accordance
with JIS K6251, and thereby a tensile strength and an elongation at
break were measured.
(7) Flame Retardancy Test
[0067] A specimen being 127 mm in length, 12.7 mm in width, and 1.5
mm in thickness was kept vertical, then a fire of burner was
brought to the bottom end of the specimen closely for 10 seconds
and the burner was taken away. The length of time taken until the
fire of the specimen went out was measured. As soon as the fire
went out, the fire of burner was again brought to the bottom end of
the specimen closely for 10 seconds. The length of time taken until
the fire of the specimen went out was measured in the same way as
the first time. In addition, it was simultaneously evaluated
whether the cotton placed under the specimen began to burn or not
due to the dropping of live charcoal on it. From the viewpoints of
how long the specimen kept burning and whether the cotton began to
burn or not in the first and second tests, the burning-rank was set
according to the UL-94V standard. The burning rank corresponding to
V-0 was represented by .circleincircle., the rank corresponding to
V-1 was represented by .largecircle., and the rank corresponding to
V-2 was represented by .DELTA.. V-2 represents the worst flame
retardancy and V-0 represents the best flame redardency. The case
that does not correspond to any rank of V-0 to V-2 was represented
by x.
[0068] Materials used in the Examples are as follows.
<Oil-Extended Ethylene-.alpha.-Olefin-Based Copolymer Rubber
(A1/C1)>
[0069] Oil extended rubber prepared by adding (C1) 100 parts by
weight of paraffinic mineral oil to (A1) 100 parts by weight of
ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber. (A1)
had the content of ethylene units of 66% by weight, the content of
propylene units of 30% by weight, and the content of
5-ethylidene-2-norbornene units of 4% by weight and had an
intrinsic viscosity of 4.5 dl/g. The oil-extended
ethylene-.alpha.-olefin-based copolymer rubber (A1/C1) had a Mooney
viscosity (ML.sub.1+4100.degree. C.) of 63.
<Component (B) Propylene-Based Polymer>
[0070] (B1) Propylene homopolymer (MFR (230.degree. C., 21.18 N)=15
g/10 min)
<Component (D) Crosslinking Agent>
[0071] (D1) Commercial name "APO-10DL" produced by Kayaku Akzo
Corporation (2,5-dimethyl-2,5-di(tert-butylperoxy)hexane diluted
with paraffinic oil (commercial name "PW-100" produced by Idemitsu
Kosan, Inc.) in a 10% concentration)
<Component (E) Halogen-Free Flame Retardant>
[0072] (E1) Product with the commercial name "ADK STAB FP-2100J"
produced by ADEKA Corporation. (phosphate)
<Component (F) Zinc Oxide>
[0073] (F1) Product with the commercial name "Zinc oxide Type II"
produced by Seido Chemical Industry Co., Ltd.
<Mixture of Halogen-Free Flame Retardant and Zinc Oxide>
[0074] (E2/F1) Product with the commercial name "ADK STAB
[0075] FP-2200" produced by ADEKA Corporation. (a mixture of a
phosphate and zinc oxide)
[0076] (E3/F1) Product with the commercial name "ADK STAB FP-2000S"
produced by ADEKA Corporation. (a mixture of a phosphate and zinc
oxide)
<Component (G) Polyhydric Compound>
[0077] (G1) Product with the commercial name "Pentarit" produced by
Koei Chemical Co., Ltd. (pentaerythritol)
[0078] (G2) Product with the commercial name "Di-Pentarit" produced
by Koei Chemical Co., Ltd. (dipentaerythritol)
Example 1
Production of Flame Retardant Thermoplastic Elastomer
Composition
[0079] A thermoplastic elastomer composition precursor was obtained
by kneading at 200.+-.10.degree. C. using a twin screw extruder
87.4% by weight of an oil-extended ethylene-.alpha.-olefin-based
copolymer rubber (A1/C1), 12.6% by weight of a propylene-based
polymer (B1), and high density polyethylene (commercial name
"HI-ZEX 1300J" produced by Prime Polymer Co., Ltd. (density=961
kg/m.sup.3, MFR=13 g/10 min)) in an amount of 2.9 parts by weight
per 100 parts by weight of the oil-extended
ethylene-.alpha.-olefin-based copolymer rubber (A1/C1) and the
propylene-based polymer (B1) in total.
[0080] Next, a thermoplastic elastomer composition was obtained by
kneading (in other words, dynamically vulcanizing) at
200.+-.10.degree. C. using a twin screw extruder 100 parts by
weight of the resulting thermoplastic elastomer composition
precursor, 3.2 parts by weight of a crosslinking agent (D1), 0.3
parts by weight of a crosslinking aid (trimethylolpropane
trimethacrylate (commercial name "Hi-Cross M-P" produced by Seiko
Chemical Co., Ltd.)), 0.1 parts by weight of an antioxidant
(commercial name "SUMILIZER GA80" produced by Sumitomo Chemical
Co., Ltd.), 0.2 parts by weight of a diazo type weathering
stabilizer (commercial name "SUMISORB 300" by Sumitomo Chemical
Co., Ltd.), and 0.2 parts by weight of a HALS type weathering
stabilizer (commercial name "TINUVIN 622" produced by Ciba
Specialty Chemicals).
[0081] Then, a flame retardant thermoplastic elastomer composition
was produced by kneading 104 parts by weight of the resulting
thermoplastic elastomer composition and 69.3 parts by weight of a
halogen-free flame retardant (E2/F1) at 200.+-.10.degree. C. using
a twin screw extruder. In other words, the amount of the
halogen-free flame retardant (E2/F1) used was 69.3 parts by weight
per 100 parts by weight of the thermoplastic elastomer composition
precursor used for the production of the thermoplastic elastomer
composition. The results of the measurement of physical properties
of the resulting flame retardant thermoplastic elastomer
composition are shown in Table 1.
Example 2
Production of Flame Retardant Thermoplastic Elastomer
Composition
[0082] Operations were conducted in the same manner as Example 1
except for adding 56.0 parts by weight of a halogen-free flame
retardant (E3/F1) instead of the halogen-free flame retardant
(E2/F1). The results of physical properties measurement are shown
in Table 1.
Example 3
Production of Flame Retardant Thermoplastic Elastomer
Composition
[0083] Operations were conducted in the same manner as Example 1
except for changing the amount of the halogen-free flame retardant
(E2/F1) to 44.6 parts by weight and further adding 2.7 parts by
weight of a polyhydric compound (G1) into the thermoplastic
elastomer composition. The results of physical properties
measurement are shown in Table 1.
(Production of Flame Retardant Thermoplastic Elastomer
composition)
[0084] Operations were conducted in the same manner as Example 3
except for changing the loading of the polyhydric compound (G1) to
6.9 parts by weight. The results of physical properties measurement
are shown in Table 1.
Example 5
Production of Flame Retardant Thermoplastic Elastomer
Composition
[0085] Operations were conducted in the same manner as Example 2
except for changing the amount of the halogen-free flame retardant
(E3/F1) to 34.7 parts by weight and further adding 1.4 parts by
weight of a polyhydric compound (G1) into the thermoplastic
elastomer composition. The results of physical properties
measurement are shown in Table 1.
Example 6
Production of Flame Retardant Thermoplastic Elastomer
Composition
[0086] Operations were conducted in the same manner as Example 5
except for incorporating 1.7 parts by weight of a polyhydric
compound (G2) instead of 1.4 parts by weight of the polyhydric
compound (G1), and further adding 1.4 parts by weight of zinc oxide
(F1). The results of physical properties measurement are shown in
Table 1.
Comparative Example 1
Production of Thermoplastic Elastomer Composition
[0087] 87.4% by weight of an oil-extended
ethylene-.alpha.-olefin-based copolymer rubber (A1/C1), 12.6% by
weight of a propylene-based polymer (B1), and high density
polyethylene (commercial name "HI-ZEX 1300)") in an amount of 2.9
parts by weight per 100 parts by weight of the oil-extended
ethylene-.alpha.-olefin-based copolymer rubber (A1/C1) and the
propylene-based polymer (B1) in total were mixed. A thermoplastic
elastomer composition was obtained by mixing 100 parts by weight of
the resulting mixture, 3.2 parts by weight of a crosslinking agent
(D1), 0.3 parts by weight of a crosslinking aid (commercial name
"Hi-Cross M-P"), 0.1 parts by weight of an antioxidant (commercial
name "SUMILIZER GA80"), 0.2 parts by weight of a diazo type
weathering stabilizer (commercial name "SUMISORB 300"), and 0.2
parts by weight of a HALS type weathering stabilizer (commercial
name "TINUVIN 622"), and then kneading (dynamically vulcanizing)
the mixture at 200.+-.10.degree. C. using a twin screw extruder.
The results of physical properties measurement are shown in Table
1.
Comparative Example 2
Production of Flame-Retardant Thermoplastic Elastomer
Composition
[0088] Operations were conducted in the same manner as Example 1
except for adding 69.3 parts by weight of a halogen-free flame
retardant (E1) instead of the halogen-free flame retardant (E2/F1).
The results of physical properties measurement are shown in Table
1.
Comparative Example 3
Production of Flame Retardant Thermoplastic Elastomer
Composition
[0089] Operations were conducted in the same manner as Comparative
Example 2 except for changing the amount of the halogen-free flame
retardant (E1) to 56.0 parts by weight. The results of physical
properties measurement are shown in Table 1.
Comparative Example 4
Production of Flame Retardant Thermoplastic Elastomer
Composition
[0090] 87.4% by weight of an oil-extended
ethylene-.alpha.-olefin-based copolymer rubber (A1/C1), 12.6% by
weight of a propylene-based polymer (B1), and high density
polyethylene (commercial name "HI-ZEX 1300)") in an amount of 2.9
parts by weight per 100 parts by weight of the oil-extended
ethylene-.alpha.-olefin-based copolymer rubber (A1/C1) and the
propylene-based polymer (B1) in total were mixed. A flame retardant
thermoplastic elastomer composition was obtained by mixing 100
parts by weight of the resulting mixture, 3.2 parts by weight of a
crosslinking agent (D1), 69.3 parts by weight of a halogen-free
flame retardant (E2/F1), 0.3 parts by weight of a crosslinking aid
(commercial name "Hi-Cross M-P"), 0.1 parts by weight of an
antioxidant (commercial name "SUMILIZER GA80"), 0.2 parts by weight
of a diazo type weathering stabilizer (commercial name "SUMISORB
300"), and 0.2 parts by weight of a HALS type weathering stabilizer
(commercial name "TINUVIN 622"), and then kneading (dynamically
vulcanizing) the mixture at 200.+-.10.degree. C. using a twin screw
extruder. The results of physical properties measurement are shown
in Table 1.
Comparative Example 5
Production of Flame-Retardant Thermoplastic Elastomer
Composition
[0091] Operations were conducted in the same manner as Comparative
Example 4 except for changing the loading of the halogen-free flame
retardant (E2/F1) to 104 parts by weight. The results of physical
properties measurement are shown in Table 1.
TABLE-US-00001 TABLE 1 Example 1 Example 2 Example 3 Example 4
Example 5 Example 6 Compounding (A1) (% by weight) 43.7 43.7 43.7
43.7 43.7 43.7 Formulation (B1) (% by weight) 12.6 12.6 12.6 12.6
12.6 12.6 (C1) (% by weight) 43.7 43.7 43.7 43.7 43.7 43.7 HI-ZEX
1300J (parts by weight) 2.9 2.9 2.9 2.9 2.9 2.9 Thermoplastic
(parts by weight) 100 100 100 100 100 100 elastomer composition
precursor (D1) (parts by weight) 3.2 3.2 3.2 3.2 3.2 3.2 (E1)
(parts by weight) (E2 + F1) (parts by weight) 69.3 44.6 44.6 (E3 +
F1) (parts by weight) 56.0 34.7 34.7 (F1) (parts by weight) 1.4
(G1) (parts by weight) 2.7 6.9 1.4 (G2) (parts by weight) 1.7
Properties Burning Text -- .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
Evaluation MFR g/10 min 7 10 60 65 19 28 Hardness -- 77 79 78 77 76
76 Strength at break MPa 3.1 3.0 3.2 2.3 5.1 4.6 Elongation at
break % 360 500 480 350 670 600 Compression set % 42 48 43 51 48 49
Comparative Comparative Comparative Comparative Comparative Example
1 Example 2 Example 3 Example 4 Example 5 Compounding (A1) (% by
weight) 43.7 43.7 43.7 43.7 43.7 Formulation (B1) (% by weight)
12.6 12.6 12.6 12.6 12.6 (C1) (% by weight) 43.7 43.7 43.7 43.7
43.7 HI-ZEX 1300J (parts by weight) 2.9 2.9 2.9 2.9 2.9
Thermoplastic (parts by weight) 100 100 100 100 100 elastomer
composition precursor (D1) (parts by weight) 3.2 3.2 3.2 3.2 3.2
(E1) (parts by weight) 69.3 56.0 (E2 + F1) (parts by weight) 69.3
104.0 (E3 + F1) (parts by weight) (F1) (parts by weight) (G1)
(parts by weight) (G2) (parts by weight) Properties Burning Text --
X .largecircle. X .circle-w/dot. .circle-w/dot. Evaluation MFR g/10
min 30 4 11 4 3 Hardness -- 60 78 74 75 80 Strength at break MPa
4.6 2.7 3.0 3.1 2.8 Elongation at break % 580 430 471 230 160
Compression set % 35 44 39 64 60
* * * * *